Synthesis control process



' c. E. STARR, JR., ErAL 2,636,904

April 28, 1953 SYNTHESIS CONTROL PROCESS Filed Feb. 28, 1950 Patented Apr. 28, 1953 SYNTHESIS CONTROL rnooass Charles E. Starr, Jr., and Elphegc M. Charlet, Baton Rouge, La., assignors to Standard Oil Development Company, a corporation of Dela- Wale Application February 28, 1950, Serial No. 146,896

The present invention relates to an improved method of controlling a process for the preparation of oxygenated organic compounds by the reaction of oleiinic compounds with hydrogen and carbon monoxide in the presence of a carbonylation catalyst. The invention is particularly concerned with a method of controllingr the indicated process effective vin obtaining a product suitable for use as a feed stock in the preparation of alcohols.

Processes are well known for synthesizing oxygenated organic compounds by the reaction of oleiinic organic compounds, carbon monoxide, and hydrogen. Suitable catalysts to be used in such a process comprise salts of a catalytically active met-a1 formed by reaction with high molecular weight organic acids. For example, such catalyst salts, or soaps, may be cobalt, or iron, oleate, stearato, naphthenate and the like. vThese salts are soluble in the liquid oleiin feed and may be supplied to the carbonylation reactor dissolved in the feed in the form of a hydrocarbon solution. In the presence of the indicated catalyst, the olenic hydrocarbons, carbon mom oxide, and hydrogen react under pressure to yield 'e' a product consisting principally of aldehydes containing one more carbon atom than the oleiinic material, together with secondary reac" tion products such as polymers, alcohols, esters, ketones, em. This oxygenated organic mixture may be used as such in order to obtain aldehydes therefrom, or more frequently is employed as the feed stream to a further treating stage in which the aldehydes are hydrogenated to correspond1 ing alcohols, or in which the aldehydes may be oxidized to corresponding carboxylic acids.

, In the operation of the process heretofore de scribed, the metal salt employed as a catalyst is substantially converted to a carbonyl compound during the carbonylation reaction. For example, in the case in which `the carbonylation process employs a salt of cobalt, the products of the reaction will contain cobalt carbonyl, In addition, the carbonylation product will contain iron carbonyl formed from reaction with iron reactors. For many purposes it is desirable, and for particular purposes such as the subsequent'hydro-` genation of this product stream, it is essential, to remove the `metal carbonylcompounds. This object may be accomplished by heating the carbonylation product stream at high temperatures, and if desired at high pressures, for a period of time so as to secure the decomposition of the metal carbonyl compounds. However, it has been found` difficult to consistently secure complete 1 claim. (ci. 26o- 604) decomposition of the metal carbonyls. As a result contamination of the final product with cobalt carbonyl and/or iron carbonyl frequently occurs.

It is, therefore, the principal object of this invention to provide an analytical method and a control process whereby metal carbonyl decomposition can be accurately, instantaneously, and continually determined and controlled so as to insure processing which will yield a metal carbonyl free product.

It is a further object of this invention to provide a commercially applicable control method for operating a carbonylation process so as to secure a metal carbonyl free product at maximum processing eiilciency.

It is a more specific object of this invention to provide a control method whereby the practical exhaustion of a reactor for decomposing metal carbonyls may be determined.

To achieve the objects of this invention, at least a portion of the final product stream of the carbonylation process, after passing through a metal carbonyl decomposing zone, is passed through an infra-red transparent analytical cell; infra-red energy of 5.0 microns and subsequently of 5.4 microns is passed through the analytical cell and through the carbonylation product contained in the cell. Infra-red energy of the indicated wave length which has passed through the cell is then caused to fall upon an infra-red energy detector developing an electrical signal. This electrical signal is then used to operate process controls associated with the metal carbonyl decomposing zone in a manner to eliminate all metal carbonyls from the final product.

The manner in which the indicated objectives of this invention, and the manner in which the briefly described method of this invention is carried out, may be more fully appreciated from the following complete description of a particular embodiment of this invention to be read in conjunction with the accompanying drawing iagrammatically illustrating a now plan of a process embodying this invention. Referring to the drawing therefore, the numeral i represents a carbonylation reactor suitable for the reaction 4of oleiins, carbon monoxide, and hydrogen in the presence of a catalyst such as cobalt naphthenate. Reactor i comprises a high pressure reaction vessel which may be either packed, or unpacked. Thus, if desired the reactor may be packed with any non-metallic packing material such as Raschig rings, porcelain pipes, ceramic mate rial, pumice and the like. The necessary reactants may be withdrawn from storage zones or reactant sources indicated by the rectangles 2, 3 and 4. Thus synthesis gas consisting of hydrogen and carbon monoxide together with a small quantity cf methane and carbon dioxide may be contained in Zone 2 for introduction to reactor I, through line 5. Similarly, zone 3 may consist of a storage zone for an olefinic composition such as a substantially pure composition consisting of C7 olefins. The oleiins may be withdrawn from zone 3 for introduction to zone I through line 6. Finally the catalyst to be employed, such as cobalt naphthenate, for example, may be maintained in zone 4 for addition to zone I through line 'I. For this purpose it is preferred that the particular catalyst be maintained in solution in a soluble solvent such as liquid parafiins, or olens, such as the C7 olens to be used in the carbonylation reaction. The stream of synthesis gas withdrawn from zone 2 and passed through line are also passed through a gas compressor 8 operative to compress the synthesis gases to the presure at which zone I is to be operated. Similarly, the olefin feed passed through line 6 is compressed in compressor 9. The synthesis gas, and the olen feed may be heated to carbonylation temperatures in any desired manner. For this purpose it is preferred to pass the olefin feed after compression and before admixture with the other reactants through a heating zone I0. This heating zone may simply consist of a fired coil operated so as to heat the olefin feed sufciently high to provide all heating requirements of the carbonylation reaction.

The olens used as reactants in the carbonylation reaction may consist of any olefinic hydrocarbons having one carbon atom less than the number of carbon atoms in the desired oxygenated product. Insofar as the synthesis gases are consumed at equivalent, or equimolar rates, synthesis gas components are usually added at equimolar proportions. If desired, however, and as disclosed by a recent patent, U. S. 2,437,600, an

excess of hydrogen may be employed. The ratio -Y of synthesis gas feed to olefin feed may vary widely but in general about 2500 to 25000 cubic feet of synthesis gas per barrel of olen feed are employed. The catalyst is employed in weight percents of about 1 to 3%.

As indicated, therefore, the indicated reactants in the indicated proportions are brought into the reactor I to undergo the carbonylation reaction. The reactor is preferably operated at a pressure of 1500-4500 p. s. i. g., and at a temperature of about 250 to 450 F., depending upon the nature of the olefin feed, and other reaction conditions. The rate of flow of synthesis gases, and olens through reactor 2 is so regulated that the desired conversion level of the olenic material is obtained. A relatively long residence time in re@ actor I, of the order of about two hours is required in the carbonylation stage. Somewhat higher throughput rates may be used to provide for a shorter residence period by employing high carbon monoxide partial pressure. Thus with a carbon monoxide partial pressure of 1500 to 2500 p. s. i. a shorter residence period may be employed. To achieve this object the hydrogen to carbon monoxide ratio may preferably be adjusted in the range of about 0.5 to 0.9.

The carbonylation reaction proceeds by virtue of the decomposition of the metallic salt, used asa catalyst, to a metal followed by the reaction of the metal with carbon monoxide to form the metal carbonyl which is the active form of the catalyst. Thereafter the metal carbonyl, such as cobalt carbonyl, catalyzes the reaction of olens with carbon monoxide and hydrogen to form the desired aldehyde containing one more carbon atom than the corresponding olefin from which it is prepared. Particularly in the carbonylation reaction in which high partial pressures of carbon monoxide are maintained, substantial concentrations of cobalt carbonyl Will be found in the eluent of reactor I withdrawn through line II. Thus the product stream from reactor I carried from the reactor through line II Will contain about 0.05 to 0.15 percent of cobalt carbonyl, or of the metal carbonyl formed from the particular catalyst used. vIn order to remove the metal carbonyl from the product stream the stream of line I I is conducted to a metal carbonyl decomposition zone I5 wherein the reactor eflluent may be heated at high temperatures and pressures for a period of time. Preferably the stream of line II is rst conducted to a cooler I2 to secure condensation of all constituents of the eiuent stream with the exception of unreacted synthesis gas. For this purpose this stream may be cooled to a temperature of about F. in zone I2. Thereafter the stream may be conducted to a gas separator I3 operated to permit the removal of unreacted synthesis gas overhead through line I4 for recycle to reactor I. The condensed liquid products are then removed from zone I3 through line IAA for introduction to the carbonyl decomposing zone I5. If desired, a portion of the liquid stream withdrawn from the bottom of zone I3 may be recycled to Zone I through line I6.

As the metal carbonyl decomposing zone I5 is operated at a high temperature, it is preferred to pass the stream of line I4A through a preheater I1 prior to lintroduction to zone I5. Heater I1 may beoperated to heat the stream to the desired decomposition temperature. Suitable temperatures may be chosen from the range of about 300 to 400 F., and suitable pressures for operation of zone I5 may be chosen from a range of about 15 to 200 lbs. p. s. i., although higher pressures may be used. It is believed thatthe indicated heating of the product stream containing the metal carbonyl is effective to decompose the metal carbonyl so as to permit free metal to plate out on interior surfaces of the decomposition Zone. As an aid to this decomposition a. stripping gas, such as a hydrogen containing gas or hydrogen may be introduced to the bottom of zone I5 through line I8 for 'removal at the top of the zone through line I9. 'Ihis stripping gas is effective to strip and removev carbon monoxide resulting from the decomposition of the metal carbonyl. Consequently,v the gas stream removed through line I9'comprises hydrogen and carbon monoxide. To provide available surface for decomposition of the metal resulting from the decomposition of the metal carbonyl, packing may be employed in zone I5.

The liquid carbonylation reaction product is maintained in zone I5 for a residence' period of about 30 minutes. The carbonylation reaction product when Withdrawn from zone I5 through line 20 is then substantially free of catalyst. Furthermore the product of line 20 is substantially free of any iron carbonyl which may have been formed from iron surfaces encountered in the preceding processing steps. It is preferred, however, to conduct the carbonylation reaction' product of line 20 to an additional heating zone;

or soaking zone 2 I wherein additional tlmeis pro# vided for the decomposition of any `metal car bonyls remaining. Thus zone 2| may he operated at temperatures of about 325 to 350 F. and presn sures of about 150 p. `s. i., to achieve this object. Thereafter the carbonylation reaction product is withdrawn from soaking zone 2l through line 22,-fcr use as desired. As indicated, vit is particularly contemplated that the carbonylation product be subjected to a subsequent 'hydrogenation treatment for the production of alcohols.

Heretoiore the general process involved in the carbonylation reaction has been described. Insofar as this process is a `conventional process,

known to the art, no Vfurther identication of this processwillbe made.

In accordance with this inventionl the car honylation `process described is improved by a control method operative to best maintain eifective operation of zones iti and 21| wherein metal carbonyls are decomposed. it has been found that in the operation oi the rectal carhonyl decomposing zone I5, diil'lculties are ireouently encountered due to incomplete decomposition of metal carbonylzs. it is presently hypothesieed that zone It may etico-tively vbe exhausted for further carbonyl decomposition when plating out of metals in Zone l5 has reached a particular stage. Consequently, periods or successful operation ci the decomposition Zone are frequently and unexi -pectcdly terminated so that metal carboni/is are, :no 'longer eiectively decomposed in zone. Heretofore it has been a difficult problem to dem termine when this stage of operation has been reached. Towards this end attempts have been made to analyze the stream of line 2u withdrawn from zone l5 so as to determine the metal carbonyl content of this stream. However, in with* drawing samples from line Eil, and in transporting these samples to ananalytical laboratory, and in conducting the necessary analysis it Vhas 'eeen found that the metal carbonyls originally present at the `time ci' sampling have decomposed. t is possible that the decomposition between the time of sampling and the actual analysis may be due to contact of the sample with sampling 1container, may be due to the period time involved, or may be due to other factors involved in sampling and transportation of the sample. in any case it has been found very di-fcultif notim-v possible to successfully withdraw samples from 'line 2d so as to permit their vanalysis for metal carbonyl content, accor, to conventional analysisfmethods. As a result, prior to the present invention operationy of decomposition tone I5 could not be followed with certainty particularly so as to readily and .immediately indicate any didiculties in the operation of zone l.

In accordance with this invention, therefore, a bleeder line 23 is conducted from line 2i! carry-` ing a sample of the product oi zone it continuously through an infra-red transparent cell. 2t. As will be brought out, by passing infrared energy of suitable Wave length through this sample cell, and by detecting the transmitted energy using a bolometer, or equivalent device, an electrical sig-- ual may be obtained proportional. to the ccnoenn tration o'i metal carbonyl present in the stream. Thus as diagrammatioally illustrated, unit t5 identified by the dashed line rectangle on the drawing, comprises an infra-red analysis ratus operated to provide an electrical signal pro-` portional to the metal carbonyl content of the stream of line 2li. If desired, the output of ele-y ment 25 may be used to control a recorder, or

other indicating device to' appraise an .operator of thefzneta'l carbonyl content :of the stream. Pref-` erably, however, the electrical signal developed 'by element .25 is conducted through conductors 2E to an automatic lcontrol mechanism 27 suitable 'for operating 4a valve in conjunction with heater il.. Thus, the pneumatic or electrical lead 3i may control a valve whichcontrols the amount of heat supplied hy heater Il to the stream of line MA fed into Zone it?. Alternatively, unit 2l maybe used in a similar fashion to control the rate of flow of the products in line it into Zone I5, The control apparatus is operated in such a manner that when lmetal carbonyl content is detected the stream 2B by 'instrument 25, the product stream flowing through line hl will be heated to a higher temperature; Kfor example, the control apparatus may be operative to cause about a 5 or 19 increase in temperature in the stream lenter ing zone I5. As a consequence of this ,change in feed stream temperature, carbonyl decomposition may be improvedin zone i5 so as to permit vobtaining a carbonyl .tree stream in line 2i).

In a preferred adaptation of this process, controller 2l includes a voltage gate operative to send a further control signal through electrical or pneumatic lead E@ `whenever the voltage developed by the control instrument 2 exceeds a particular value. For exemple, the voltage ygate of unit 2l may be set so that when unit ITE had been caused to heat the input stream ci line I5 by an .incre ment of `more than about 10 F., a signal will then he passed through. line 2t operative to controla level control 35 associated with the soaking tant; 2l. By this means the time during which the carbonylaticn product is retained in soaking zone 2l may be increased.

As a further provision of the process of this invention when the level in soaking tank 2l has been increased to ainaximum, by control of unit 2l, provision is made to completely remove `decomposing zone l5 from the process, and to vom ploy an alternative decomposition zone 35,. Thus. a iioat control tl may be positioned in the upper part or Zone 2i so that when the liquid level .in zone 2l reaches the float, an electrical sv .ch can be thrown which will close a solenoid valve or equivalent mechanism 38 in line lli so as to pass the product of line lll into zone in .a .similar .fashion other valves in the eiluent lines from zone I5 and 35, and vin the hydrogen input lines i8 and 3Q may be operated so as to remove decoro-,- posing zone l5 from the process, and so as to l employ .decomposing zone By this means it is possible to remove vzone l5 from the treating vprocess whenever the Zone has become in such a co'ndition as to no longer effectively decompose metal carbonyls. This Zone may then he regenerated and reconditioned while zone 36 is being used in a similar manner,

In its broadest application, therefore, the present invention relates to the use of infra-red energy of a particular wave length to irradiate the stream, or a portion oi the stream flowing through line 28. In accordance with the infrared transmitting properties of this stream at the particular wave length employed, an infra-red detector of the apparatus 25 may be caused to provide an electrical signal proportional in mag nitude to the metal carbonyl content of the product in line 2Q. In the preferred utilization of this electrical signal for control purposes, control apparatus is utilized responsive to the electrical signal so as to increase the temperature existing in zone I5 in order to increase the decomposition of metal carbonyl. As a second step of the control process, when the ytemperature of zone I has been changed by a given increment, for example in this manner, a second control operation is initiated resulting in the increase in soaking time of the product passed through soaking zone 2l. This is best achieved by increasing the level of the material maintained in zone 2|. Finally as a third step of the control method when the level in zone 2l has reached a maximum, decomposition zone l5 is switched oif stream and a fresh decomposition zone 36 is switched on stream. By the control method described, it has been found possible to achieve the greatest efliciency in metal carbonyl decomposition utilizing a given decomposition zone and associated soaking Zone for the greatest practical length of time without possibility of contaminating the final carbonylation product with metal carbonyls.

As indicated, in the operation of this control method a critical Wave length of infra-red energy must be employed. In the case in which the catalyst employed in the carbonylation reactor consists of iron carbonyl, the frequency which must be used is 5.0 microns. In the preferred case in which cobalt carbonyl is used as the catalyst, the infra-red energy must be 5.4 microns. These critical wave lengths have been found to be unique portions of the infra-red spectrum where infra-red transmission will solely be a function of iron or cobalt carbonyl concentration independent of the infra-red transmission characteristics of any of the other constituents present in stream 20. Thus, the composition of stream while consisting principally of aldehydes having one carbon atom more than the initial olen feed, will also contain alcohols, esters, ketones, hemi-acetals, acetals and unsaturated compounds. insofar as each of these constituents have absorption bands in the infra-red spectrum', a complicated problem has existed in suitably identifying metal carbonyl content in the presence of these constituents. As indicated, however, it has been found that at infra-red Wave lengths of 5.0 and 5.4 microns for iron and cobalt carbonyl respectively, infra-red transmission will be free of interference from the other infra-red adsorbing constituents of the stream.

Suitable control apparatus for use in the method described may be provided by those skilled in the art. Thus the infra-red analysis instrument may consist of an infra-red source, a monochromator adjusted to transmit infra-red energy having a Wave length of 5.0 or 5.4 microns,

ilo

and an infra-red detector such as a thermocou-f ple, or a bolometer, to develop an electrical signal proportional to the infra-red transmission through the sample cell of the apparatus. Alternatively, if desired, a conventional type of double beam infra-red control apparatus may be employed utilizing constituents in the cells of vthe apparatus so as to permit transmission of 5.0, or 5.4 micron infra-red energy. Control unit 21 operative to convert the electrical signal-from element 25 to a -control electrical signal or pneumatic signal may consist of conventional control apparatus such as a Brown electronic circular chart potentiometer, calibrated to a special range to meet conditions of application. Similarly, the electrically, or pneumatically controlled valves associated with heatery Il, or positioned in line I4 are of conventional construction such as a Masoneilan diaphragm control valve, model 37. Finally, the level control associated with soaking zone 2| may be of the type such as a Brown Air-O-Line liquid level control.

What is claimed is:

In a carbonylation reaction process in which olens, hydrogen and carbon monoxide are reacted to provide aldehydes in the presence of a cobalt catalyst and in which a cobalt carbonyl decomposing zone is provided, and in which a soaking tank is employed, the improvement which comprises passing the eiiiuent of the said decomposition zone through an infra-red transparent cell, passing infra-red energy of 5.4 microns Wave length through the said cell, impinging trans-v mitted infra-red energy on an infra-red detector developing voltages proportional to the carbonyl content of the said effluent stream, said voltages having a first and second order of magnitude, increasing the extent of heating the said decomposition zone in response to voltages of the rst magnitude, and increasing the level of material maintained in the soaking drum in response to voltages of the second magnitude.

CHARLES E. STARR, JR. ELPHEGE M. CHARLET.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,386,830 Wright Oct. 16, 1945 2,386,831 Wright Oct. 16, 1945 2,459,404 Anderson, Jr. Jan. 18, 1949 2,462,946 Coggeshall et al. Mar. 1, 1949 2,462,995 Ritzmann Mar. 1, 1949 2,504,682 Harlan, Jr. Apr. 18, 1950 

